CN115737931A - 3D printing bone tissue repair scaffold material and preparation method thereof - Google Patents
3D printing bone tissue repair scaffold material and preparation method thereof Download PDFInfo
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- sodium alginate
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- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 70
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
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Abstract
The invention discloses a 3D printing bone tissue repair scaffold material and a preparation method thereof, and relates to a scaffold material body, wherein MXene (Ti) is carried on biphase calcium phosphate of the scaffold material body 3 C 2 ) And berberine, and is prepared by cross-linking with sodium alginate, such as biphase calcium phosphate, sodium alginate, MXene (Ti) 3 C 2 ) The weight ratio of berberine to berberine is 60: 6: 0.025-0.125:0.05, the biphase calcium phosphate material is a mixture of hydroxyapatite and beta-tricalcium phosphate, and the stent material body has a mutually-communicated macro-pore structure with the pore diameter of 300 mu m. Disclosure of the inventionThe 3D printing bone tissue repair scaffold material and the preparation method thereof have the advantages that biphase calcium phosphate, sodium alginate, MXene (Ti 3C 2) and berberine are used as raw materials, and the material has good biocompatibility and bone repair property.
Description
Technical Field
The invention relates to the technical field of biomedical materials, in particular to a 3D printing bone tissue repair scaffold material and a preparation method thereof.
Background
Bone tissue is an important component of the human body and plays an important role in maintaining the normal physiological functions of the human body. In smaller defects bone tissue may heal spontaneously without external intervention. However, when the bone defect is large in range, the bone defect is often repaired by a transplantation operation. At present, autologous bone is still the gold standard for bone graft repair due to its high histocompatibility, non-immunogenicity and excellent bone regeneration performance. However, injury to the donor site and the accompanying complications such as inflammation and hematoma limit the success rate of transplant surgery. In addition, autograft is still unable to meet the bone repair requirements, limited by the quality of bone tissue and the amount of bone harvested from the donor area. Allogeneic bone may be associated with immune rejection and disease transmission.
In order to overcome the defects of the existing treatment means, the development of an ideal bone defect replacement and repair material is an important subject in the technical field of biomedical materials. Bone tissue engineering has made great progress over the past decades, however its application in the clinic still faces many problems: the prosthesis is difficult to give consideration to mechanical property and porosity; the degradation rate is not controllable; the precision is poor, and the individuation is lacked; the antibacterial property is insufficient, the infection rate is high, and the like, and the preparation of the bone tissue restoration relates to multiple interdisciplinary specialties, and the technical difficulty is high, so the breakthrough is needed.
Disclosure of Invention
The invention discloses a 3D printing bone tissue repair scaffold material and a preparation method thereof, aiming at solving the problem that the restoration provided in the background technology is difficult to take mechanical property and porosity into account; the degradation rate is not controllable; the precision is poor, and individuation is lacked; the antibacterial property is insufficient, the infection rate is high, and the like, and the preparation of the bone tissue restoration relates to multiple interdisciplinary specialties, and the technical difficulty is high, so the technical problem to be broken through is solved.
In order to achieve the purpose, the invention adopts the following technical scheme:
A3D-printed bone tissue repair scaffold material comprises a scaffold material body, wherein MXene (Ti) is carried on biphase calcium phosphate of the scaffold material body 3 C 2 ) And berberine, and is prepared by cross-linking with sodium alginate, such as biphase calcium phosphate, sodium alginate, MXene (Ti) 3 C 2 ) The weight ratio of berberine to berberine is 60: 6: 0.025-0.125:0.05, the biphase calcium phosphate material is a mixture of hydroxyapatite and beta-tricalcium phosphate, and the stent material body has a mutually-communicated macro-pore structure with the pore diameter of 300 mu m.
A preparation method of a 3D printing bone tissue repair scaffold material specifically comprises the following steps:
s1: preparing a sodium alginate solution of 60 mg/ml;
s2: preparing 100mg/ml berberine-dimethyl sulfoxide solution;
s3: according to the mass ratio of the berberine to the sodium alginate of 0.05:6, adding the berberine-dimethyl sulfoxide solution of 100mg/ml in the step S2 into the sodium alginate solution of 60mg/ml in the step S1, and fully and uniformly mixing to obtain a mixed solution;
s4: and (3) adding the biphasic calcium phosphate into the mixed solution obtained in the step (S3) in a fractional manner according to the mass ratio of the biphasic calcium phosphate to the sodium alginate of 60: 6, and fully and uniformly mixing to obtain mixed slurry of the biphasic calcium phosphate, the sodium alginate, the berberine and the deionized water in a mass ratio of 60: 6: 0.05: 100.5.
S5: preparing MXene (Ti) 25-125mg/ml 3 C 2 ) Solution, ultrasound;
s6: according to MXene (Ti) 3 C 2 ) And sodium alginate in a mass ratio of 6:0.025 to 0.125, adding the solution obtained in e) to S4Mixing the slurry, and mixing to obtain biphase calcium phosphate, sodium alginate, and MXene (Ti) 3 C 2 ) The mass ratio of the berberine to the deionized water is 60: 6: 0.025-0.125:0.05:101.5 of mixed slurry;
s7: preparing a calcium chloride solution with the mass fraction of 30%;
s8: designing a three-dimensional structural model of the stent by using three-dimensional modeling software, printing the stent layer by using the mixed slurry in the step S6 as printing ink by adopting an extrusion type 3D printing technology, and then soaking the stent into the calcium chloride solution obtained in the step S7 to form a porous stent material with a stable structure;
s9: carrying out freeze drying treatment on the porous scaffold material obtained in the step S8;
s10: and (3) performing later biological characterization, namely placing the porous scaffold material obtained in the step S9 in 808nm laser with the laser power range of 0.2-0.8W/cm < 2 >, and irradiating for 10-15min.
In a preferred embodiment, the specific method of the step S2 is as follows: dissolving berberine powder in dimethyl sulfoxide solution, and performing ultrasonic treatment for 1h to prepare 100mg/ml berberine-dimethyl sulfoxide solution, wherein the specific method in the step S3 comprises the following steps: according to the mass ratio of the berberine to the sodium alginate of 0.05:6, adding the 100mg/ml berberine-dimethyl sulfoxide solution in the step S2 into the 60mg/ml sodium alginate solution in the step S1, and stirring the mixture for 24 hours on a magnetic stirrer (40 ℃/200 rpm) to prepare a mixed solution, wherein the specific method in the step S4 comprises the following steps: uniformly adding the biphase calcium phosphate powder into the mixed solution obtained in the step S3 by 3 times according to the mass ratio of the biphase calcium phosphate to the sodium alginate of 60: 6, and fully and uniformly mixing by using a defoaming instrument after 20g of biphase calcium phosphate is added each time, wherein the modes are as follows: mixing at 500rpm/0.5min, mixing at 2000rpm/5min, and defoaming at 2500rpm/0.5min to obtain biphase calcium phosphate, sodium alginate, berberine and deionized water at a mass ratio of 60: 6: 0.05:100.5, the specific method of the step S5 is as follows: MXene (Ti) 3 C 2 ) Dissolving the powder in deionized water, and performing ultrasonic treatment for 2h to obtain MXene (Ti) 25-125mg/ml 3 C 2 ) The solution, the specific method of the S6 step is as follows: according to MXene (Ti) 3 C 2 ) And sodium alginate in a mass ratio of0.025-0.125: and 6, adding the solution obtained in the step 5 into the mixed slurry obtained in the step 4, fully mixing the solution by using a deaerator, and adopting the following mode: mixing at 500rpm/0.5min, mixing at 2000rpm/5min, defoaming at 2500rpm/0.5min to obtain biphase calcium phosphate, sodium alginate and MXene (Ti) 3 C 2 ) The mass ratio of berberine to deionized water is 60: 6: 0.025-0.125:0.05:101.5 of mixed slurry.
From the above, the 3D printing bone tissue repair scaffold material comprises a scaffold material body, wherein MXene (Ti) is carried on biphase calcium phosphate of the scaffold material body 3 C 2 ) And berberine, and is prepared by cross-linking with sodium alginate, such as biphase calcium phosphate, sodium alginate, MXene (Ti) 3 C 2 ) The weight ratio of berberine to berberine is 60: 6: 0.025-0.125:0.05, the biphase calcium phosphate material is a mixture of hydroxyapatite and beta-tricalcium phosphate, and the stent material body has a mutually-communicated macro-pore structure with the pore diameter of 300 mu m. The 3D printing bone tissue repair scaffold material and the preparation method thereof provided by the invention have the following technical effects:
the invention uses biphase calcium phosphate, sodium alginate, MXene (Ti 3C 2) and berberine as raw materials, and has better biocompatibility and bone repairability.
MXene (Ti 3C 2) and berberine are added into printing ink, the photo-thermal reaction and the drug release performance of the stent are endowed, and the accurate regulation and control of the photo-thermal reaction and the release of the antibacterial drug of the stent are achieved by changing the proportion of all components of the slurry and the later laser excitation power density, so that the photo-thermal regulation and control of the antibacterial function of the stent are realized.
And (III) the 3D printing manufacturing technology is adopted, so that high-precision morphological restoration and biological function reconstruction of individual bone defects can be realized, and the cell tissue ingrowth and nutrient exchange are promoted by accurately regulating and controlling the size of macroscopic pores.
And fourthly, crosslinking the scaffold by utilizing a chelating reaction between sodium alginate and calcium chloride (calcium ions), and enhancing the form stability and the mechanical property of the scaffold after printing.
And (V) treating the scaffold after the freeze drying technology is adopted, so that a secondary micro-pore structure of the scaffold can be further formed, and a multi-stage pore bioactive bone repair scaffold with macro macropores and micro micropores distributed alternately is formed.
Drawings
Fig. 1 is a schematic overall structure diagram of a 3D-printed bone tissue repair scaffold material according to the present invention.
Fig. 2 is a flowchart of a preparation method of a 3D printed bone tissue repair scaffold material according to the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
Referring to fig. 1, the 3D printed bone tissue repair scaffold material comprises a scaffold material body, wherein MXene (Ti) is carried on biphase calcium phosphate of the scaffold material body 3 C 2 ) And berberine, and is prepared by cross-linking with sodium alginate, such as biphase calcium phosphate, sodium alginate, MXene (Ti) 3 C 2 ) The weight ratio of berberine to berberine is 60: 6: 0.025-0.125:0.05, the biphase calcium phosphate material is a mixture of hydroxyapatite and beta-tricalcium phosphate, and the stent material body has a mutually-communicated macro-pore structure with the pore diameter of 300 mu m.
Referring to fig. 2, a preparation method of a 3D printed bone tissue repair scaffold material specifically includes the following steps:
s1: preparing a sodium alginate solution of 60 mg/ml;
s2: preparing 100mg/ml berberine-dimethyl sulfoxide solution;
s3: according to the mass ratio of the berberine to the sodium alginate of 0.05:6, adding the berberine-dimethyl sulfoxide solution of 100mg/ml in the step S2 into the sodium alginate solution of 60mg/ml in the step S1, and fully and uniformly mixing to obtain a mixed solution;
s4: and (2) adding the biphasic calcium phosphate into the mixed solution obtained in the step (S3) in a ratio of 60: 6 by mass of the biphasic calcium phosphate to the sodium alginate, and fully and uniformly mixing to obtain mixed slurry of the biphasic calcium phosphate, the sodium alginate, the berberine and the deionized water in a ratio of 60: 6: 0.05:100.5 by mass.
S5: preparing MXene (Ti) 25-125mg/ml 3 C 2 ) Solution, ultrasonic treatment;
s6: according to MXene (Ti) 3 C 2 ) And sodium alginate in a mass ratio of 6:0.025-0.125, adding the solution obtained in e) into the mixed slurry in S4, and fully mixing to obtain biphase calcium phosphate, sodium alginate and MXene (Ti) 3 C 2 ) The mass ratio of the berberine to the deionized water is 60: 6: 0.025-0.125:0.05:101.5 of mixed slurry;
s7: preparing a calcium chloride solution with the mass fraction of 30%;
s8: designing a three-dimensional structural model of the stent by using three-dimensional modeling software, printing the stent layer by using the mixed slurry in the step S6 as printing ink by adopting an extrusion type 3D printing technology, and then immersing the stent into the calcium chloride solution obtained in the step S7 to form a porous stent material with a stable structure;
s9: carrying out freeze drying treatment on the porous scaffold material obtained in the step S8;
s10: and (3) performing later biological characterization, namely placing the porous scaffold material obtained in the step S9 in 808nm laser with the laser power range of 0.2-0.8W/cm < 2 >, and irradiating for 10-15min.
In a preferred embodiment, the specific method of the step S1 is as follows: dissolving sodium alginate powder in deionized water, and stirring on a magnetic stirrer (40 ℃/200 rpm) for 24h to obtain a 60mg/ml sodium alginate solution.
In a preferred embodiment, the specific method of the step S2 is as follows: dissolving berberine powder in dimethyl sulfoxide solution, and performing ultrasonic treatment for 1 hr to obtain 100mg/ml berberine-dimethyl sulfoxide solution.
In a preferred embodiment, the specific method of the step S3 is as follows: according to the mass ratio of the berberine to the sodium alginate of 0.05:6, adding the 100mg/ml berberine-dimethyl sulfoxide solution in the step S2 into the 60mg/ml sodium alginate solution in the step S1, and stirring the mixture for 24 hours on a magnetic stirrer (40 ℃/200 rpm) to prepare a mixed solution.
In a preferred embodiment, the specific method of the step S4 is as follows: uniformly adding the biphase calcium phosphate powder into the mixed solution obtained in the step S3 by 3 times according to the mass ratio of the biphase calcium phosphate to the sodium alginate of 60: 6, and fully and uniformly mixing by using a defoaming instrument after 20g of biphase calcium phosphate is added each time, wherein the modes are as follows: mixing at 500rpm/0.5min, mixing at 2000rpm/5min, and defoaming at 2500rpm/0.5min to obtain biphase calcium phosphate, sodium alginate, berberine and deionized water at a mass ratio of 60: 6: 0.05:100.5 of mixed slurry.
In a preferred embodiment, the specific method of step S5 is: mixing MXene (Ti) 3 C 2 ) Dissolving the powder in deionized water, and performing ultrasonic treatment for 2h to obtain MXene (Ti) 25-125mg/ml 3 C 2 ) And (3) solution.
In a preferred embodiment, the specific method of the step S6 is: according to MXene (Ti) 3 C 2 ) And sodium alginate in a mass ratio of 0.025-0.125: and 6, adding the solution obtained in the step 5 into the mixed slurry obtained in the step 4, fully mixing the solution by using a deaerator, and adopting the following mode: mixing at 500rpm/0.5min, mixing at 2000rpm/5min, defoaming at 2500rpm/0.5min to obtain biphase calcium phosphate, sodium alginate and MXene (Ti) 3 C 2 ) The mass ratio of the berberine to the deionized water is 60: 6: 0.025-0.125:0.05:101.5 of mixed slurry.
The printing ink is prepared by taking biphase calcium phosphate as a matrix material, MXene (Ti 3C 2) and berberine are added into the printing ink, so that the photothermal reaction and the drug release capability of the bone repair material are endowed, and the photothermal and drug release performance of the bone repair material is regulated and controlled by regulating the proportion of each component in the printing ink, so that the regulation and control of the antibacterial function of the material are realized. The three-dimensional printing technology is used as a manufacturing mode, the macroscopic pore size of the stent is controlled, and the regulation and control of the release of the antibacterial drugs are increased. And the scaffold is processed by a freeze drying technology at the later stage to form a multi-level pore structure with macro macropores and micro micropores alternately distributed, so that the biological activity of the scaffold is further enhanced.
Example 1:
dissolving sodium alginate powder in deionized water, and stirring for 24h on a magnetic stirrer (40 ℃/200 rpm) to obtain 100ml of sodium alginate solution with the concentration of 60 mg/ml; adding 0.5ml berberine-dimethyl sulfoxide solution with concentration of 100mg/ml, and stirring on a magnetic stirrer (40 deg.C/200 rpm) for 24 hr to obtain mixed solution; adding 20g of biphase calcium phosphate powder into the mixed solution, and fully and uniformly mixing in a deaerator (mode: 500rpm/0.5min for mixing, 2000rpm/5min for mixing, 2500rpm/0.5min for deaerating); repeating the operation for 2 times, and finally adding 60g of biphase calcium phosphate; adding 1ml of MXene (Ti 3C 2) solution with the concentration of 75mg/ml, putting the solution in a deaerator, fully and uniformly mixing the solution (mode: 500rpm/0.5min mixing, 2000rpm/5min mixing and 2500rpm/0.5min deaerating) to obtain printing slurry, wherein the mass ratio of the biphase calcium phosphate, the sodium alginate and the MXene (Ti 3C 2) to the berberine and the deionized water is 60: 6: 0.075:0.05:101.5; printing the porous bone repair scaffold by using an extrusion type 3D printing instrument; immersing the stent into a 30% calcium chloride solution, and crosslinking for 24 hours at room temperature; washing the bracket with deionized water for 3 times; putting the bracket into a freeze dryer for freeze drying for 48h; and during later characterization, the sample is irradiated under a laser (0.5W/cm & lt 2 & gt) of 808nm for 10min. Finally obtaining the 3D printing bone tissue repair scaffold with the photothermal regulation and control antibacterial function. The scaffold obtained by the embodiment has good photo-thermal reactivity and drug controlled release property, and shows stronger antibacterial property and osteogenic activity.
Example 2:
printing paste is prepared and a stent is printed according to the configuration method of the embodiment 1, and after the stent is immersed in calcium chloride solution for crosslinking, the stent is subjected to freeze drying treatment to obtain the stent, and laser irradiation is carried out during characterization. The preparation process and parameters of the stent are the same as those of embodiment 1, except that in this embodiment, the ratio of the printing slurry used in embodiment 1 is adjusted to be biphase calcium phosphate, sodium alginate and MXene (Ti 3C 2), and the mass ratio of berberine to deionized water is 60: 6: 0.025:0.05:101.5, the rest of the treatment is the same as that described in example 1. Compared with the embodiment 1, in the embodiment, as the solid content of MXene (Ti 3C 2) in the printing slurry is lower, the content of MXene (Ti 3C 2) in the bone tissue repair scaffold with the photothermal regulation and antibacterial functions is lower, the photothermal reaction performance of the scaffold is further reduced, and the regulation and control performance of photothermal on drug release is reduced. Therefore, the effective pectin for regulating the antibacterial function of the scaffold by photo-thermal treatment obtained in the embodiment 1 is poor, namely the scaffold has a poorer antibacterial effect than the scaffold in the embodiment 1 under the same irradiation time and power density.
Example 3:
printing paste is prepared and a stent is printed according to the configuration method of the embodiment 1, and after the stent is immersed in calcium chloride solution for crosslinking, the stent is subjected to freeze drying treatment to obtain the stent, and laser irradiation is carried out during characterization. The preparation process and parameters of the stent are the same as those of embodiment 1, except that in this embodiment, the ratio of the printing slurry used in embodiment 1 is adjusted to be biphase calcium phosphate, sodium alginate and MXene (Ti 3C 2), and the mass ratio of berberine to deionized water is 60: 6: 0.125:0.05:101.5, the rest of the treatment is the same as that described in example 1. Compared with the embodiment 1, in the embodiment, as the solid content of MXene (Ti 3C 2) in the printing slurry is higher, the content of MXene (Ti 3C 2) in the bone tissue repair scaffold with the photothermal regulation and antibacterial functions is higher, so that the photothermal reaction performance of the scaffold is enhanced, and the regulation and control performance of photothermal on drug release is improved. Therefore, the effective pectin for regulating the antibacterial function of the scaffold by photo-thermal treatment obtained in the embodiment 1 is good, that is, the scaffold has better antibacterial effect than the scaffold in the embodiment 1 under the condition of the same irradiation time and power density.
Example 4:
printing paste is prepared and a stent is printed according to the configuration method of the embodiment 1, and after the stent is immersed in calcium chloride solution for crosslinking, the stent is subjected to freeze drying treatment to obtain the stent, and laser irradiation is carried out during characterization. The preparation process and parameters of the stent are the same as those of embodiment 1, except that in this embodiment, the ratio of the printing slurry used in embodiment 1 is adjusted to be biphase calcium phosphate, sodium alginate and MXene (Ti 3C 2), and the mass ratio of berberine to deionized water is 80: 6: 0.075:0.02:101.5, the rest of the treatment is the same as that described in example 1. Compared with the embodiment 1, in the embodiment, because the solid content of the berberine in the printing slurry is less, the berberine content in the bone tissue repair scaffold with the photothermal regulation and antibacterial functions is lower, so that the release amount of the berberine is too small, and the antibacterial effect of the medicine is reduced. Therefore, the stent drug obtained in this example had a poorer antibacterial effect than that of example 1.
Example 5:
printing paste is prepared and a stent is printed according to the configuration method of the embodiment 1, and after the stent is immersed in calcium chloride solution for crosslinking, the stent is subjected to freeze drying treatment to obtain the stent, and laser irradiation is carried out during characterization. The preparation process and parameters of the stent are the same as those of embodiment 1, except that in this embodiment, the mixture ratio of the printing slurry used in embodiment 1 is adjusted to be biphase calcium phosphate, sodium alginate and MXene (Ti 3C 2), and the mass ratio of berberine to deionized water is 80: 6: 0.075:0.08:101.5, the rest of the treatment is the same as that described in example 1. Compared with the embodiment 1, in the embodiment, due to the fact that the solid content of the berberine in the printing slurry is high, the berberine in the bone tissue repair scaffold with the photothermal regulation and antibacterial functions is high, so that the released amount of the berberine is excessive, and although the antibacterial property of the scaffold drug is enhanced, the scaffold drug has a certain toxic effect on osteogenesis related cells. Therefore, the stent drug obtained in this example has better antibacterial effect than that of example 5.
Example 6:
printing paste is prepared and a stent is printed according to the configuration method of the embodiment 1, and after the stent is immersed in calcium chloride solution for crosslinking, the stent is subjected to freeze drying treatment to obtain the stent, and laser irradiation is carried out during characterization. The stent preparation process and parameters were the same as in example 1, except that the laser power density was changed to 0.25W/cm2 in this example as characterized in example 1. The remaining treatment was the same as described in example 1. Compared with the embodiment 1, in the embodiment, the laser power density is weakened, so that the balance temperature of the bone tissue repair scaffold with the photothermal regulation and control antibacterial function is reduced, and thus the photothermal antibacterial property and the regulation and control property of photothermal on drug release of the scaffold are weakened in the embodiment. It showed a poorer antibacterial effect than example 1.
Example 7:
printing paste is prepared and a stent is printed according to the configuration method of the embodiment 1, and after the stent is immersed in calcium chloride solution for crosslinking, the stent is subjected to freeze drying treatment to obtain the stent, and laser irradiation is carried out during characterization. This example changed the laser power density to 0.75W/cm2 when characterized in example 1. The remaining treatment was the same as described in example 1. Compared with the embodiment 1, the embodiment has the advantages that the laser power density is increased, so that the balance temperature of the bone tissue repair scaffold with the photothermal regulation and antibacterial functions is increased, although the photothermal antibacterial property of the scaffold is enhanced, a certain damage effect is shown on osteoblasts due to overhigh temperature, and the bone tissue repair is not facilitated. Therefore, the photo-thermal antibacterial property and the photo-thermal regulation and control property of the drug release of the stent are weakened. It showed better antibacterial effect than example 6.
Comparative example 1:
dissolving sodium alginate powder in deionized water, and stirring for 24h on a magnetic stirrer (40 ℃/200 rpm) to obtain 100ml of sodium alginate solution with the concentration of 60 mg/ml; adding 0.5ml of deionized water, and stirring for 24 hours on a magnetic stirrer (40 ℃/200 rpm); adding 20g of biphase calcium phosphate powder into the mixed solution, and fully and uniformly mixing in a deaerator (mode: 500rpm/0.5min for mixing, 2000rpm/5min for mixing, 2500rpm/0.5min for deaerating); repeating the operation for 2 times, and finally adding 60g of biphase calcium phosphate; adding 1ml of deionized water, fully and uniformly mixing in a deaerator (mode: 500rpm/0.5min mixing, 2000rpm/5min mixing, 2500rpm/0.5min deaerating) to obtain printing slurry, wherein the mass ratio of the biphase calcium phosphate, the sodium alginate and the MXene (Ti 3C 2) to the berberine to the deionized water is 60: 6: 0:0:101.5; printing the porous bone repair scaffold by using an extrusion type 3D printing instrument; immersing the stent in a 30% calcium chloride solution, and crosslinking for 24 hours at room temperature; washing the bracket with deionized water for 3 times; putting the bracket into a freeze dryer for freeze drying for 48h; and during later characterization, the sample is irradiated under a laser (0.5W/cm & lt 2 & gt) of 808nm for 10min. Finally obtaining the 3D printing bone tissue repair scaffold. Compared with example 1, in this example, since the scaffold does not contain MXene (Ti 3C 2) and berberine, the scaffold has only osteogenic activity, and does not have photothermal reactivity, controlled drug release property and antibacterial property.
Comparative example 2:
printing paste is prepared and a stent is printed according to the configuration method of the embodiment 1, and after the stent is immersed in calcium chloride solution for crosslinking, the stent is subjected to freeze drying treatment to obtain the stent, and laser irradiation is carried out during characterization. The preparation process and parameters of the stent are the same as those of embodiment 1, except that in this embodiment, the ratio of the printing slurry used in embodiment 1 is adjusted to be biphase calcium phosphate, sodium alginate and MXene (Ti 3C 2), and the mass ratio of berberine to deionized water is 60: 6: 0:0.05:101.5, the rest of the treatment is the same as that described in example 1. Compared with example 1, in this example, since the scaffold does not contain MXene (Ti 3C 2), the scaffold has only osteogenic activity and weak drug antibacterial property, and has no photothermal reactivity and drug controlled release property.
Comparative example 3:
according to the preparation method of the embodiment 1, printing slurry is prepared, a support is printed, the support is immersed into calcium chloride solution for crosslinking, then freeze drying treatment is carried out, and the support is obtained and is irradiated by laser during characterization. The preparation process and parameters of the stent are the same as those of embodiment 1, except that in this embodiment, the mixture ratio of the printing slurry used in embodiment 1 is adjusted to be biphase calcium phosphate, sodium alginate and MXene (Ti 3C 2), and the mass ratio of berberine to deionized water is 60: 6: 0.075:0:101.5, the rest of the treatment is the same as that described in example 1. Compared with example 1, in this example, since the scaffold does not contain berberine, the scaffold has only osteogenic activity, photothermal reactivity and photothermal antibacterial property, but does not have controlled drug release property and drug antibacterial property.
Comparative example 4:
printing paste is prepared and a stent is printed according to the configuration method of the embodiment 1, and after the stent is immersed in calcium chloride solution for crosslinking, the stent is subjected to freeze drying treatment to obtain the stent, and laser irradiation is carried out during characterization. The preparation process and parameters of the stent are the same as those of embodiment 1, except that in this embodiment, the mixture ratio of the printing slurry used in embodiment 1 is adjusted to be biphase calcium phosphate, sodium alginate and MXene (Ti 3C 2), and the mass ratio of berberine to deionized water is 60: 6: 0.0125:0.05:101.5, the rest of the treatment is the same as that described in example 1. Compared with the embodiment 1, in the embodiment, as the solid content of MXene (Ti 3C 2) in the printing slurry is too low, the content of MXene (Ti 3C 2) in the bone tissue repair scaffold with the photothermal regulation and antibacterial functions is too low, so that the photothermal reaction performance of the scaffold is too weak, the requirement on the laser power density is too high, and the requirement exceeds the treatment threshold. Therefore, the practicability of the photothermal control antibacterial function of the stent obtained in the embodiment is poorer than that of the embodiment 1.
Comparative example 5:
printing paste is prepared and a stent is printed according to the configuration method of the embodiment 1, and after the stent is immersed in calcium chloride solution for crosslinking, the stent is subjected to freeze drying treatment to obtain the stent, and laser irradiation is carried out during characterization. The preparation process and parameters of the stent are the same as those of embodiment 1, except that in this embodiment, the ratio of the printing slurry used in embodiment 1 is adjusted to be biphase calcium phosphate, sodium alginate and MXene (Ti 3C 2), and the mass ratio of berberine to deionized water is 60: 6: 0.25:0.05:101.5, the rest of the treatment is the same as that described in example 1. Compared with the embodiment 1, in the embodiment, as the solid content of MXene (Ti 3C 2) in the printing slurry is too high, the content of MXene (Ti 3C 2) in the bone tissue repair scaffold with the photothermal regulation and antibacterial functions is too high, and although the photothermal reaction performance of the scaffold is enhanced, the too high content of MXene (Ti 3C 2) has certain toxicity on osteoblast-related cells and is not beneficial to bone tissue repair. Therefore, the scaffold obtained in this example has a poorer effect in the application of the scaffold in bone tissue repair than that of example 1.
Comparative example 6:
printing paste was prepared and the stent was printed according to the configuration method of example 1, and freeze-dried to obtain a stent, which was irradiated with laser light at the time of characterization. The stent preparation process and parameters were the same as in example 1, except that the stent was not crosslinked by calcium ion, i.e., freeze-dried after printing and molding, and the rest of the process was the same as in example 1. Compared with the embodiment 1, in the embodiment, because the scaffold is not subjected to crosslinking treatment, a crosslinked network structure is lacked in the structure, the mechanical property of the scaffold is poor after freeze drying, and the scaffold is easy to scatter in the application process, so that the scaffold structure is damaged. Therefore, the scaffold obtained in this example was not feasible for use in bone tissue repair as in example 1.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (8)
1. The 3D-printed bone tissue repair scaffold material comprises a scaffold material body, and is characterized in that MXene (Ti) is carried by biphase calcium phosphate of the scaffold material body 3 C 2 ) And berberine, and is prepared by cross-linking with sodium alginate, such as biphase calcium phosphate, sodium alginate, MXene (Ti) 3 C 2 ) The weight ratio of berberine to berberine is 60: 6: 0.025-0.125:0.05, the biphase calcium phosphate material is a mixture of hydroxyapatite and beta-tricalcium phosphate, and the stent material body has a mutually-communicated macro-pore structure with the pore diameter of 300 mu m.
2. A preparation method of a 3D printing bone tissue repair scaffold material is characterized by comprising the following steps:
s1: preparing a sodium alginate solution of 60 mg/ml;
s2: preparing 100mg/ml berberine-dimethyl sulfoxide solution;
s3: according to the mass ratio of the berberine to the sodium alginate of 0.05:6, adding the berberine-dimethyl sulfoxide solution of 100mg/ml in the step S2 into the sodium alginate solution of 60mg/ml in the step S1, and fully and uniformly mixing to obtain a mixed solution;
s4: adding the biphasic calcium phosphate into the mixed solution obtained in the step S3 in a manner of multiple times according to the mass ratio of the biphasic calcium phosphate to the sodium alginate of 60: 6, and fully and uniformly mixing to obtain mixed slurry of the biphasic calcium phosphate, the sodium alginate, the berberine and the deionized water in a mass ratio of 60: 6: 0.05: 100.5;
s5: preparing MXene (Ti) 25-125mg/ml 3 C 2 ) Solution, ultrasonic treatment;
s6: according to MXene (Ti) 3 C 2 ) And sodium alginate in a mass ratio of 6:0.025-0.125, adding the solution obtained in e) into the mixed slurry in S4, and fully mixing to obtain biphase calcium phosphate, sodium alginate and MXene (Ti) 3 C 2 ) The mass ratio of the berberine to the deionized water is 60: 6: 0.025-0.125:0.05:101.5 of mixed slurry;
s7: preparing a calcium chloride solution with the mass fraction of 30%;
s8: designing a three-dimensional structural model of the stent by using three-dimensional modeling software, printing the stent layer by using the mixed slurry in the step S6 as printing ink by adopting an extrusion type 3D printing technology, and then soaking the stent into the calcium chloride solution obtained in the step S7 to form a porous stent material with a stable structure;
s9: carrying out freeze drying treatment on the porous scaffold material obtained in the step S8;
s10: and (3) performing later biological characterization, namely placing the porous scaffold material obtained in the step S9 in 808nm laser with the laser power range of 0.2-0.8W/cm < 2 >, and irradiating for 10-15min.
3. The preparation method of the 3D printing bone tissue repair scaffold material according to claim 2, wherein the specific method of the S1 step is as follows: dissolving sodium alginate powder in deionized water, and stirring on a magnetic stirrer (40 ℃/200 rpm) for 24h to obtain a 60mg/ml sodium alginate solution.
4. The preparation method of the 3D printing bone tissue repair scaffold material according to claim 3, wherein the specific method of the S2 step is as follows: dissolving berberine powder in dimethyl sulfoxide solution, and performing ultrasonic treatment for 1 hr to obtain 100mg/ml berberine-dimethyl sulfoxide solution.
5. The preparation method of the 3D printing bone tissue repair scaffold material according to claim 4, wherein the specific method of the S3 step is as follows: according to the mass ratio of the berberine to the sodium alginate of 0.05:6, adding the 100mg/ml berberine-dimethyl sulfoxide solution in the step S2 into the 60mg/ml sodium alginate solution in the step S1, and stirring the mixture for 24 hours on a magnetic stirrer (40 ℃/200 rpm) to prepare a mixed solution.
6. The preparation method of the 3D printing bone tissue repair scaffold material according to claim 5, wherein the specific method of the S4 step is as follows: uniformly adding the biphase calcium phosphate powder into the mixed solution obtained in the step S3 by 3 times according to the mass ratio of the biphase calcium phosphate to the sodium alginate of 60: 6, and fully and uniformly mixing by using a defoaming instrument after 20g of biphase calcium phosphate is added each time, wherein the modes are as follows: mixing at 500rpm/0.5min, mixing at 2000rpm/5min, and defoaming at 2500rpm/0.5min to obtain biphase calcium phosphate, sodium alginate, berberine and deionized water at a mass ratio of 60: 6: 0.05:100.5 of the mixed slurry.
7. The preparation method of the 3D printing bone tissue repair scaffold material according to claim 6, wherein the specific method of the step S5 is as follows: mixing MXene (Ti) 3 C 2 ) Dissolving the powder in deionized water, and performing ultrasonic treatment for 2h to obtain 25-125mg/ml MXene (Ti) 3 C 2 ) And (3) solution.
8. The preparation method of the 3D printing bone tissue repair scaffold material according to claim 6, wherein the specific method of the S6 step is as follows: according to MXene (Ti) 3 C 2 ) And sodium alginate in a mass ratio of 0.025-0.125: and 6, adding the solution obtained in the step 5 into the mixed slurry obtained in the step 4, fully mixing the solution by using a deaerator, and adopting the following mode: mixing at 500rpm/0.5min, mixing at 2000rpm/5min, defoaming at 2500rpm/0.5min to obtain biphase calcium phosphate, sodium alginate and MXene (Ti) 3 C 2 ) The mass ratio of the berberine to the deionized water is 60: 6: 0.025-0.125:0.05:101.5 of mixed slurry.
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